Production of biodiesel from sunflower oil and ethanol by base catalysed transesterification Production of biodiesel from sunflower oil and ethanol by base catalyzed transesterification MSc Thesis Alejandro Sales Department of Chemical Engineering Royal Institute of Technology (KTH) Stockholm, Sweden June 2011 Production of biodiesel from sunflower oil and ethanol by base catalysed transesterification Production of biodiesel from sunflower oil and ethanol by base catalyzed transesterification MSc Thesis Alejandro Sales Supervisor Rolando Zanzi Vigouroux Department of Chemical Engineering Royal Institute of Technology (KTH) Stockholm, Sweden Examiner Joaquín Martínez Department of Chemical Engineering Royal Institute of Technology (KTH) Stockholm, Sweden June 2011 Abstract Biodiesel is an attractive alternative fuel for diesel engines.The feedstock for biodiesel production is usually vegetable oil, pure oil or waste cooking oil, or animal fats The most common way today to produce biodiesel is by transesterification of the oils with an alcohol in the presence of an alkaline catalyst. It is a low temperature and low‐pressure reaction. It yields high conversion (96%‐98%) with minimal side reactions and short reaction time. It is a direct conversion to biodiesel with no intermediate compounds. This work provides an overview concerning biodiesel production. Likewise, this work focuses on the commercial production of biodiesel. The Valdescorriel Biodiesel plant, located in Zamora (Spain), is taken like model of reference to study the profitability and economics of a biodiesel plant. The Valdescorriel Biodiesel plant has a nominal production capacity of 20000 biodiesel tons per year. The initial investment for the biodiesel plant construction is the 4.5 millions €. The benefits are 2 million €/year. The return of investment is calculated in less than 3 years. A biodiesel of 98% can be reached. The energy used for the biodiesel production is 30% less than the obtained energy from the produced biodiesel. Replacing petro diesel by the biodiesel produced in the plant, a significant CO2 reduction can be reached (about 48%). It means that the CO2 emission can be reduced by 55 000 tons CO2 per year. The production of biodiesel from sunflower oil and ethanol using sodium hydroxide as catalyst was performed in the laboratory and the results are discussed. The results are analyzed using the statistic method of Total Quality. The effect of the ethanol/oil ratio and the amount of used catalyst on the yield of biodiesel as well as on the properties of the produced biodiesel is studied. In the experimental part the density, viscosity and refractive index of the produced biodiesel are measured. The ethanol/oil ratio influences the biodiesel production. The yield of biodiesel increases with the ethanol/oil ratio. Regarding the influence of the amount of catalyst on biodiesel production in the studied conditions, an increase of the biodiesel yield with the amount of catalyst can be appreciated. The study of the evolution of the transesterification during time shows that a reaction time of one hour is sufficient enough in order to reach the highest yield of biodiesel. Production of biodiesel from sunflower oil and ethanol by base catalysed transesterification Sammanfattning Biodiesel är ett attraktivt alternativt bränsle för diesel motorer. Biodiesel framställs vanligtvis ur vegetabilisk olja, avfall matolja, eller animaliska fetter. Det vanligaste sättet idag för att producera biodiesel är genom omförestring av oljor med en alkohol i närvaro av en alkalisk katalysator. Det är en reaktion vid låg temperatur och lågt tryck. Den ger ett högt utbyte (96 % -98 %) med få sidoreaktioner vid kort reaktionstid. Arbetet ger en översikt om produktionen av biodiesel. Likaså fokuserar detta arbete på den kommersiella produktionen av biodiesel. En ekonomisk studie ingår där lönsamhet och ekonomi för en biodieselanläggning beräknas. Valdescorriel biodieselanläggning, som ligger i Zamora (Spanien), tas som modell för studie. Produktionskapacitet på Valdescorriel biodieselanläggning beräknas till 20 000 biodiesel ton per år. Den inledande investeringen för biodieselanläggning byggande är 4,5 miljoner €. Avkastning är 2 miljoner € / år. Investeringen kan återbetalas på mindre än 3 år. Utbyte för biodiesel kan komma upp till 98 %. Den energi som används för att producera biodiesel är 30 % mindre än den erhållna energin från den producerade biodiesel. Genom att ersätta fossil biodiesel med biodiesel som produceras i anläggningen kan CO2-utsläpp minskas med 48 %. Det innebär att utsläpp CO2 kan reduceras med 55 000 ton per år. Framställning av biodiesel från solrosolja och ethanol med natriumhydroxid som katalysator utfördes i laboratoriet och resultaten diskuteras. Resultaten analyseras med hjälp av statistik metoden för kvalitetsstyrning (Total Quality). Effekten av förhållande ethanol/olja och mängden använd katalysator på utbyte samt på egenskaperna hos den framställda biodieseln studeras. De egenskaper som studeras hos biodiesel är densitet, viskositet och brytningsindex. Det ethanol/olja förhållandet påverkar utbyte och egenskaper hos den framställda biodieseln. Utbyte av biodiesel ökar med förhållande ethanol/olja. Angående påverkan av mängden katalysatorer på biodiesel framställning i den studerade villkor är det inte möjligt att få en definitiv slutsats. Men det har visat sig en tendens till ökad biodiesel utbyte med mängd katalysator. Försök syftande att studera hur omförestring utvecklas under tiden visar att det är tillräckligt med en reaktionstid på 1 timme för att uppnå högsta möjliga utbyte av biodiesel. Production of biodiesel from sunflower oil and ethanol by base catalysed transesterification Acknowledgement I sincerely thank my supervisor, Prof. Rolando Zanzi, for giving me the opportunity to do this research work, and because, he has offered me an endless number of facilities since the beginning. I would like also thank all people in the Chemical Technology Department of KTH for their support and make the stay so pleasant. And the Chemical engineer, Mr. José Luciano González, who works in the Valdescorriel Biodiesel Plant for provide as much information. My last but not least thanks goes to the Exchange Erasmus Program for offering me this great opportunity. In that sense, I am very grateful to the Kungliga Tekniska Högskolan (KTH) and to the Universidad Politécnica de Valencia (UPV). Thank you. Contents 1. Introduction ............................................................................................................................... 2 1.1 Biofuels ................................................................................................................................ 2 1.2 Historical evolution ............................................................................................................. 3 1.3World trade .......................................................................................................................... 4 1.4 Biodiesel .............................................................................................................................. 4 1.5 Biodiesel Production ........................................................................................................... 5 1.6 Biodiesel features .............................................................................................................. 11 2. Biodiesel plant profitability ..................................................................................................... 13 2.1 Mass flow .......................................................................................................................... 21 2.2 Economic analysis ............................................................................................................. 23 2.3. Calculation and comparison of greenhouse gas emissions .............................................. 25 3. Experimental ........................................................................................................................... 27 3.1 Experimental Procedure .................................................................................................... 27 3.2 Equipments ....................................................................................................................... 28 3.3 Chemicals & Security ......................................................................................................... 29 3.4 Methods of Data Analysis ................................................................................................. 29 3.5 Results and discussion ....................................................................................................... 34 a. Effects on Yield of produced biodiesel ......................................................................... 34 b. Effects on the density of the produced biodiesel ....................................................... 38 c. Effects on the viscosity of the produced biodiesel ..................................................... 42 d. Effects on the refractive index of the produced biodiesel .......................................... 44 Prediction model ................................................................................................................. 48 Yield: .................................................................................................................................... 48 Density and viscosity: .........................................................................................................